Apparatus for and method of forming thin film

ABSTRACT

A thin film forming apparatus has an evaporation source for emitting a cluster beam, an ionizing device for irradiating the cluster beam from the evaporation source with thermal electrons, thereby forming cluster ions, an accelerating device for accelerating the cluster ions so as to irradiate a substrate with the cluster ions together with neutral clusters, and cluster ion rate control device for periodically varying the rate of irradiation of the substrate with the cluster ions at a period which is longer than the time required for the cluster ions to reach the substrate from the ionizing device and which is shorter than the time required for forming a mono-atom or mono-molecular layer on the substrate, thereby controlling the time-mean of the rate of irradiation with the cluster ions.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an apparatus for forming a thin film by evaporation on a substrate by cluster ion beam evaporation technique and also to a method of forming a thin film.

2. Description of the Related Art

FIG. 4 is a schematic sectional view of a known thin film forming apparatus disclosed, for example, in Japanese Patent Publication No. 54-9592, while FIG. 5 is a partly-sectioned perspective view of the apparatus shown in FIG. 4.

Referring to these Figures, a vacuum exhausting device (not shown) is connected to a discharge passage 2 annexed to a vacuum tank 1. A bed plate 4 is fixed to the bottom of the vacuum tank 1 through a plurality of pillars 3. A crucible 8 is mounted on the bed plate 4 through the intermediary of a support bar 5, insulating support member 6 and a crucible support 7. The crucible 8 is charged with a material 9 which is to be evaporated and deposited, e.g., copper (Cu). One or more nozzles 8b, each having a diameter of 1 to 2 mm, are connected to a lid 8a of the crucible 8.

A heating filament 10 for heating the crucible 8 surrounds the latter. A heat shield plate 11 is provided around the filament 10. The crucible 8, heating filament 10, heat shield plate 11 and a power supply (not shown) in cooperation form an evaporation source 12 which forms a cluster beam 27.

A thermal electron emitting portion 13, which emits ionizing thermal electrons 14, is disposed above the evaporation source 12. The thermal electron emitting portion 13 includes an ionizing filament 15, and an electron extracting electrode 16 which extracts thermal electrons 14 from the ionizing filament 15 and applies the extracted thermal electrons 14 to a cluster beam 27. A heat shielding plate 17 for shielding radiated heat is disposed around the filament 15. The thermal electron emitting portion 13, a power supply (not shown) for the thermal electron emitting portion 13, and the heat shielding plate 17 in cooperation form ionizing means 18 which ionizes the cluster beam 27 to generate cluster ions 28.

An accelerating electrode 19 disposed above the ionizing means 18 is adapted to be activated by an accelerating power supply (not shown) so as to establish a potential difference between itself and the electrode 16. Accelerating means 30 is composed of the accelerating electrode 19 and the accelerating power supply.

The heat shielding plates 11, 17, the electron extraction electrode 16 and the acceleration electrode 19 are supported in an insulated manner by an insulating support member 20 which in turn is supported on the bed plate 4 through a supporting post 21 and an insulator 22. A substrate 23 is carried by a substrate holder 24 which is secured to the top of the vacuum vessel 1 through insulators 25. Thus, the substrate is disposed at upper portion of the space inside the vacuum vessel 1.

In the use of this known thin film forming apparatus, the crucible 8 is charged with the material 9 to be evaporated, and the interior of the vacuum vessel 1 is evacuated to a high degree of vacuum, e.g., 10⁻⁴ Pa or so(about 10⁻⁶ Torr). Subsequently, the heating filament 10 is energized to generate heat, so that the crucible 8 is heated by collision with thermal electrons and by radiation heat, whereby the evaporation material 9 is evaporated. The heating of the crucible 8 is conducted to such an extent that the vapor pressure of the evaporation material of about 10 to 10³ Pa (0.1 to several tens of Torr.). In this state, due to adiabatic expansion caused by the difference in the pressure between interior and exterior of the crucible 8, many atoms are loosely aggregated to form a bulk of atoms, i.e., clusters 26, thus producing the cluster beam 27.

The cluster beam 27 is irradiated with thermal electrons 14 emitted from the ionizing filament 15. Consequently, an atom in a certain cluster in the cluster beam 27 is ionized to form a cluster ion 28. The cluster ion 28 thus formed is moderately accelerated by the electric field formed between the accelerating electrode 19 and the electron extracting electrode 16, and collides with the substrate 23 together with non-ionized neutral cluster 6, whereby a thin film is deposited on the substrate 23.

In the known method for ionizing the cluster beam 27, the ionizing current produced by the thermal electrons 14 is a D.C. current and is kept constant during evaporation. Therefore, the amount of the cluster ions on the substrate 3 is determined by the level of the ionizing current which is initially set when the evaporation deposition is commenced.

FIG. 6 is a diagram showing the relationship between substrate radius and the cluster ion current density, illustrative of an example of ion current density as measured on the substrate 23 when the evaporation deposition was conducted by the known ionizing method. The evaporation deposition was conducted by using copper as the evaporation material 9 at an evaporation deposition rate of 24 nm/min and accelerating current of 1.5 kV, while varying the level of the ionizing current. The measurement of the cluster ion current was conducted by moving a Faraday cup of an aperture size of 3.6 mm within a horizontal plane 400 mm above the crucible 8. From the current density distribution of the cluster ions on the substrate 23, it is understood that the cluster ions 28 tend to concentrate to the central region of the substrate 23 when the level of the ionizing current is small and that cluster ions 28 on the peripheral portion of the substrate 23 increase as the level of the ionizing current becomes higher.

Thus, in the described known thin film forming apparatus of the present invention, there is no means for varying the amount of cluster ions on the central region of the substrate, although the amount of cluster ions on the peripheral region of the same is controllable by changing the level of the ionizing current. It has been difficult to adequately control the characteristics of the thin film such as affinity of the film to the substrate and crystallinity of the same by a control of the amount of the cluster ions, particularly when the substrate 23 used has a large area.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide a thin film forming apparatus and method capable of uniformly controlling the amount of cluster ions irradiating the surface of a substrate over the entire area of the substrate, thereby overcoming the above-described problems of the prior art.

To this end, according to one aspect of the present invention, there is provided a thin film forming apparatus, comprising: an evaporation source for emitting a cluster beam; ionizing means for irradiating the cluster beam from the evaporation source with thermal electrons to form cluster ions; accelerating means for accelerating the cluster ions so as to irradiate a substrate with the cluster ions together with neutral clusters; and cluster ion rate control means for periodically varying the rate of irradiation of the substrate with the cluster ions at a period which is longer than the time required for the cluster ions to reach the substrate from the ionizing means and which is shorter than the time required for forming a mono-atom or mono-molecular layer on the substrate, thereby controlling the time-mean of the rate of irradiation with the cluster ions.

According to another aspect of the present invention, there is provided a method of forming a thin film, comprising the steps of: emitting a cluster beam from an evaporation source into a space inside a vacuum vessel; irradiating the cluster beam with thermal electrons so as to form a cluster ion; accelerating the cluster ion to enable the cluster ion to irradiate a substrate together with neutral clusters; and periodically varying the rate of irradiation of the substrate with the cluster ions at a period which is longer than the time required for the cluster ions to reach the substrate from the ionizing means and which is shorter than the time required for forming a mono-atom or mono-molecular layer on the substrate, thereby controlling the time-mean of the rate of irradiation with the cluster ions.

The above and other objects, features and advantages of the present invention will become clear from the following description of the preferred embodiments when the same is read in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustration of an embodiment of the thin film forming apparatus of the present invention;

FIG. 2 is a circuit diagram showing the major portion of ionizing means incorporated in the apparatus of FIG. 1;

FIG. 3 is a diagram showing, by way of example, the results of measurement o the ion current density distribution in the embodiment;

FIG. 4 is a sectional view of a known thin film forming apparatus;

FIG. 5 is a perspective view of the major part of the apparatus shown in FIG. 4; and

FIG. 6 is a diagram showing, by way of example, the results of measurement of the ion current density distribution in the known apparatus.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A preferred embodiment of the present invention will be described with reference to the accompanying drawings.

Referring to FIG. 1, there is shown a thin film forming apparatus of the present invention which has a basic construction similar to that of the conventional apparatus explained before in connection with with FIG. 4. Namely, the apparatus embodying the present invention employs: a vacuum vessel 1, a discharging passage 2, a crucible 8, a nozzle 8b, an evaporation material 9, a heating filament 10, a heat shield plate 11, an evaporation source 12, a thermal electron emitting portion 13, an ionizing filament 15, an electron extracting electrode 16, a heat shielding pate 17, an acceleration electrode 19, a substrate 23,, and an accelerating means 30. Thermal electrons, cluster beam and cluster ions are respectively denoted by 14, 27 and 28, as in FIG. 4.

Referring to the drawings, a heating power supply 31 is connected to the heating filament 10. An elecron-impacting power supply 32 applies a voltage of 1 kV or so between the crucible 8 and the heating filament 10, so that the crucible 8 is heated by impacting by the electrons. Thus, in the illustrated embodiment, an evaporation source 12 is composed of the crucible 8, heating filament 10, heat shielding plate 11, heating filament power supply 31 and the electron-impacting power supply 32.

An ionizing filament power supply 33 is connected to the ionizing filament 15. An ionizing thermal electron extracting power supply 34 (referred to as "ionizing power supply" hereafter) applies, between the ionizing filament 15 and the electron extracting electrode 16, ionizing voltage in the form of rectangular wave. The ionizing power supply 34 is composed of a D.C. power supply portion 34a capable of supplying a D.C. current at maximum voltage of 500V and maximum current of 1A or so, and a rectangular wave forming portion 34b. The frequency and duty of the rectangular wave are controlled by a pulse generator 35 which delivers, in an insulating manner through a signal transmission system 36, signals commanding the frequency and the duty to the rectangular wave forming portion 34b. In this embodiment, therefore, the cluster ion amount control means 40 is composed of a rectangular wave forming portion 34b, the pulse generator 35 and the signal transmission system 36.

A high voltage is applied by the accelerating electrode power supply 37 between the electron extracting electrode 16 and the accelerating electrode 19, so as to extract cluster ions 28 from the ionizing means 50 and to accelerate the extracted cluster ions. Thus, in the illustrated embodiment, an accelerating means 30 includes the accelerating electrode 19 and the accelerating electrode power supply 37. A cluster ion beam source power supply 38 is thus composed of the aforesaid power supplies 31, 32, 33, 34 and 37. In this embodiment, the ionizing means 50 includes the ionizing filament 15, electron extracting electrode 16, heat shielding plate 17, ionizing filament power supply 33, ionizing power supply 34, pulse generator 35 and the signal transmission system 36.

FIG. 2 is a circuit diagram illustrating the circuitry of a portion of the ionizing means 50 shown in FIG. 1. The signal transmission system 36 includes an optical transmitter 36a, optical fibers 36b and an optical receiver 36c. The output from the optical receiver 36c is input to one of the input terminals of an operation amplifier 42 in the rectangular wave forming portion 34b, via an input terminal 41a of the ionizing power supply 34. The ionizing power supply 34 has a first output terminal 41b for connection to the electron extracting electrode 16 and a second output terminal 41c for connection to the ionizing filament 15. A D.C. power supply 34a is connected between these output terminals 41b and 41c, so as to apply therebetween an ionizing voltage, i.e., a voltage for extracting thermal electrons.

An FET 43 for forming a rectangular pulse is connected in parallel with the D.C. power supply 34a. The FET 43 becomes in on to short-circuit between the output terminals 41b and 41c when the gate voltage thereof is 0. An output terminal of the operation amplifier 42 is connected to the gate terminal of the FET 43. The FET 43 becomes in off in response to the pulse signal (negative voltage) from the operation amplifier 42 to apply the voltage of the D.C. power supply 34a between the output terminals 41b and 41c as a pulse voltage.

A resistor 44 is connected in series to the D.C. power supply 34a. A capacitor 45 is connected to the D.C. power supply 34a in parallel therewith. The resistor 44 is intended for protecting the D.C. power supply 34a from short-circuiting when the FET 43 is in on or conductive state. In the illustrated embodiment, a 2 kΩ resistor of 200W is used as the resistor 44. The capacitor 45 is intended for making steep the rise or leading edge of the pulse derived from the D.C. power supply 34a. A capacitor of 20 μF is used in this embodiment.

The operation is as follows. As the first step, the ionizing filament 15 is energized so as to heat the same to a temperature high enough to cause a discharge of thermal electrons 14 at a sufficiently large rate. Subsequently, a reference signal in the form of a train of rectangular wave signals, having a period of 1 msec to 100 sec and a duty ratio of 1 to 100%, are generated by the pulse generator 35, and are input to the rectangular wave forming portion 34b of the ionizing power supply 34 via the signal transmission system 36. The reference signal thus input is amplified by the operation amplifier 42 to an amplitude large enough to drive the FET 43. The amplified signal is then delivered as a gate signal to the gate terminal of the FET 43. The gate signal turns on and off the electrical conduction between the source and the drain of the FET 43, whereby ionizing voltage in the form of rectangular pulses is generated between the output terminals 41b and 41c.

Consequently, ionizing voltage in the form of rectangular wave having the maximum voltage of 50 to 500V is applied between the ionizing filament 15 and the electron extracting electrode 16, whereby thermal electrons 14 are intermittently extracted. The thermal electrons 14 are then applied to the cluster beam 27, whereby cluster ions 28 are formed. Other portions of the operation are materially the same as those in the known apparatus.

As is well known, the cluster ion beam (ICB) evaporation method is a method which controls the rate of supply of the cluster ions so as to control characteristic of the thin film formed on the substrate. More specifically, the cluster ions 28 reaching the substrate 23 perform various functions such as removal of adsorbed impurities, formation of nucleus and compound reactions. These effects are obtainable even if the cluster ions 28 reach the substrate intermittently, provided that formation of a mono-atom (or mono-molecular) layer on the substrate 23 has not been completed. In general, the time required for a mono-atom or mono-molecular film to be formed on the substrate 23 is much longer than the time over which the cluster ions 28 fly before reaching the substrate. It is. therefore possible to control the rate of supply of ions, i.e., the irradiation rate, within the period of formation of mono-atom or mono-molecular layer, by intermittently extracting thermal electrons 14 as in the described embodiment.

FIG. 3 illustrates, by way of example, the results of measurement of ion current density distribution on the substrate 23, as obtained for a variety of values of the duty ratio which is the ratio of the effective part of the ionizing voltage, thus showing the relationship between the radius of area on the substrate and the density of the cluster ion current. The measurement was conducted while setting the accelerating voltage to 1.5 kV and the evaporation rate to 25 nm/min, with the period of the rectangular wave set to 10 msec. The ionizing voltage and the ionizing current were respectively set to 300V and 400 mA, respectively. An evaluation facility similar to that explained before in connection with with FIG. 6 was employed in the measurement of the cluster ion current. It is to be noted, however, an ammeter sensitive to even very small current, having a time constant sufficiently large as compared with the period of the rectangular wave, was used in order to measure the cluster ion current as a mean value over a certain period of time.

In the illustrated embodiment of the thin film forming apparatus, it is possible to extract thermal electrons 14 at such a rate as to enable a large quantity of cluster ions 28 to be formed in the ionizing means 50, by setting the level of the ionizing current to a level high enough to enable such extraction of thermal electrons 14. Consequently, the cluster ions 28 are made to diverge by the space-charge effect, so as to be applied to the entire area of the substrate 23. Conversely, when no thermal electron is being extracted, the rate of irradiation of the substrate 23 with the cluster ions 28 is substantially zero. The time-mean value of the quantity of cluster ions 28 applied to the substrate 23 is therefore substantially proportional to the duty ratio of the rectangular waveform. It is therefore possible to set the time-mean value of the rate of supply of the cluster ions 28 to the substrate 23 to a desired level, by supplying the ionizing voltage in the form of a train of rectangular wave or pulses of a predetermined period, while varying the duty of the pulse. Consequently, the rate of cluster ions 28 applied to the entire surface of the substrate 23 can be controlled as desired without impairing uniformity, whereby the characteristics of thin film can easily be controlled.

It is necessary that the period of the rectangular wave of the ionizing voltage is determined to be longer than the time required for the cluster ion 28 to fly from the ionizing filament 15 to the substrate 23 but to be shorter than the period required for forming a mono-atom (or mono-molecular) layer on the substrate 23. The required intermittent supply of cluster ions 28 cannot be attained if the period of the ionizing voltage pulse is shorter than the flying time of each cluster ion 28, whereas, the period of ionizing voltage pulse exceeding the period required for the formation of mono-atom or mono-molecular layer may cause formation of a layer which completely lacks cluster ion 28.

The time required for the cluster ion 28 to reach the substrate 23 is approximately calculated by the following formula shown in a magazine VACUUM TECHNOLOGY, pp 375, published from Kyoritu Syuppan in 1987:

    t=L{m/(2eV)}.sup.1/2

where, t represents the time of the flight of cluster ion 28, L indicates the distance between the ionizing filament 15 to the substrate 23, m represents the mass of the cluster ion 28, e represents elementary charge, and V represents the accelerating voltage for accelerating the cluster ion 28.

It is assumed here that a cluster ion composed of 100 copper atoms is accelerated by accelerating voltage of 1.5 kV to fly a distance L of 400 mm. In such a case, the flight time t is approximately 60μsec. In order to intermittently form cluster ions, it is necessary to employ, as the ionizing voltage, a rectangular wave voltage of a period longer than the above-mentioned flight time t.

On the other hand, the time required for forming a mono-atom layer on the substrate 23 is approximately calculated on the basis of the diameter of the atom. For instance, since the diameter of copper atom is 0.26 nm (2.6Å), the time required for depositing one atom layer is calculated to be about 2.6 second when the evaporation deposition rate is 6 nm/min (1Å/sec) and about 16 m sec when the evaporation deposition rate is 1 μm/min.

The length of a layer of YBa₂ Cu₃ O_(x) which is an oxide superconducting material, as measured in the direction of C-axis, is calculated to be 0.117 nm. The time required for depositing this film is calculated to be about 12 sec when the evaporation deposition rate is 6 nm/min and about 70 msec when the evaporation deposition rate is 1 μm/min.

From these estimated values, it is understood that the period of the rectangular waveform of the ionizing voltage is to be determined to range between 100 Åsec and 10 sec, in accordance with the physical properties of the material.

A description will now be given of the space-charge effect produced in the ionizing means 50. In general, an electrode system for extracting and accelerating cluster ions 28 employs an electric field lens. When the beam current formed by the ion beam passing through the electric field lens is small, the ion beam is essentially converged. However, when the beam current is so large that space-charge effect is not negligible, the ion beam is made to diverge.

In other words, when a large amount of cluster ions 28 is formed by the ionizing means 50, the beam of the cluster ions 28 diverges without being converged on the center of the substrate 23, whereby the cluster ions 28 are uniformly distributed on the substrate 23. It is predicted from the flight time of the cluster ions 28 that, in the ionizing means 50 having a length of several tens of millimeters, space-charge effect occurs on the order of microseconds. Therefore, cluster ions 28 are uniformly distributed over the area of the substrate 23 by virtue of the space-charge effect, even when the cluster ions are formed intermittently as in the described embodiment.

The temperature of heating by the ionizing filament 15 must be set such that a large quantity of cluster ions 28 are generated and that the loci of the cluster ions diverge to realize a uniform distribution of the cluster ions 28 on the substrate 23. For instance, assuming that the ionizing filament 15 has a tungsten wire which is 0.7 mm in diameter and 200 mm in length, heating is conducted by supplying electric current of about 25 A so as to develop a heating temperature of about 2500K. In such a case, ionizing current formed by the thermal electrons 14 is on the order of 400 to 800 mA, when the ionizing voltage of 100 to 400V.

In the described embodiment, cluster ions 28 are formed intermittently by applying an ionizing voltage of rectangular waveform between the ionizing filament 15 and the ion extracting electrode 16, while applying a predetermined acceleration voltage between the electron extracting electrode 16 and the accelerating electrode 19. This, however, is not exclusive and the present invention may be carried out by periodically changing the accelerating voltage while continuously forming cluster ions by the ionizing means.

This can be achieved by modifying the apparatus of FIG. 1 such that the accelerating electrode 19 is connected, instead of being grounded as described before, to an accelerating electrode power supply having a cluster ion amount control means 40 and capable of applying a high voltage having a rectangular waveform, and that the ionizing power supply is constituted by the constant-voltage D.C. power supply 34a alone. In a thin film forming apparatus having such a construction, the rate of cluster ions extracted from the ionizing means can be controlled by varying the duty of the rectangular wave from the accelerating electrode power supply, while setting the ionizing current of, for example, 400 mA. This arrangement also enables control of the rate of supply of the cluster ions to the substrate 23 while attaining a uniform current density distribution on the substrate.

Although copper is specifically mentioned as the evaporation material 9 in the described embodiments, the invention does not exclude the use of other materials as the evaporation material. It is also possible to use, for example, a multi-ICB device.

Although the ionizing voltage and accelerating voltage used in the described embodiments have rectangular waveforms, it is to be understood that other suitable waveforms may be employed provided that such waveforms enable control of the duty ratio or effective voltage. For instance, it is possible to use saw-tooth waveform, trapezoidal waveform or sine waveform. When a sine waveform is used, the effective voltage can be increased by applying a bias voltage. 

What is claimed is:
 1. A thin film forming apparatus, comprising:an evaporation source for emitting a cluster beam; ionizing means for irradiating the cluster beam from said evaporation source with thermal electrons to form cluster ions; accelerating means for accelerating the cluster ions so as to irradiate a substrate with the cluster ions together with neutral clusters; and cluster ion rate control means for periodically varying the rate of irradiation of said substrate with said cluster ions at a period which is longer than the time required for said cluster ions to reach said substrate from said ionizing means and which is shorter than the time required for forming a mono-atom or mono-molecular layer on said substrate, thereby controlling the time-mean of the rate of irradiation with said cluster ions.
 2. A thin film forming apparatus according to claim 1, wherein said ionizing means includes a ionizing filament for emitting thermal electrons, ionizing filament power supply for supplying said ionizing filament with electrical power, an electron extracting electrode for extracting thermal electrons emitted from said ionizing filament, and an ionizing power supply for applying a voltage between said ionizing filament and said electron extracting electrode.
 3. A thin film forming apparatus according to claim 2, wherein said cluster ion rate control means is adapted to periodically change the voltage applied by said ionizing power supply between said ionizing filament and said electron extracting electrode and to control the ratio of the effective portion of waveform of said voltage.
 4. A thin film forming apparatus according to claim 3, wherein said cluster ion rate control means is adapted to periodically change the voltage applied by said ionizing power supply between said ionizing filament and said electron extracting electrode, said voltage being applied in a rectangular waveform and to control the duty ratio of the rectangular waveform of said voltage.
 5. A thin film forming apparatus according to claim 4, wherein said cluster ion rate control means includes a pulse generator for generating a train or pulses indicative of the frequency and duty ratio of said rectangular waveform, a signal transmission system or transmitting pulses generated by said pulse generator, and a rectangular waveform forming circuit for changing, in accordance with the pulses transmitted through said signal transmission system, the voltage applied by said ionizing power supply between said ionizing filament and said electron extracting electrode into said voltage of said rectangular waveform.
 6. A thin film forming apparatus according to claim 5, wherein said signal transmission system includes an optical transmitter connected to said pulse generator, an optical receiver connected to said rectangular waveform forming circuit, and optical fibers connected between said optical transmitter and said optical receiver.
 7. A thin film forming apparatus according to claim 2, wherein said accelerating means includes an accelerating electrode disposed between said electron extracting electrode and said substrate, and an accelerating power supply which applied an accelerating voltage between said accelerating electrode and said electron extracting electrode so as to accelerate said cluster ion.
 8. A thin film forming apparatus according to claim 7, wherein said cluster ion rate control means is adapted to periodically change the accelerating voltage applied by said accelerating power supply between said accelerating electrode and said electron extracting electrode and to control the ratio of the effective portion of the waveform of said accelerating voltage.
 9. A method of forming a thin film; comprising the steps of:emitting a cluster beam from an evaporation source into a space inside a vacuum vessel; irradiating said cluster beam with thermal electrons so as to form a cluster ion; accelerating said cluster ion to enable said cluster ion to irradiate a substrate together with neutral clusters; and periodically varying the rate of irradiation of said substrate with said cluster ions at a period which is longer than the time required for said cluster ions to reach said substrate from said ionizing means and which is shorter than the item required for forming a mono-atom or mono-molecular layer on said substrate, thereby controlling the time-mean of the rate of irradiation with said cluster ions.
 10. A method of forming a thin film according to claim 9, wherein the control of the time-mean of the rate of irradiation with said cluster ions is conducted by intermittently ionizing said cluster beam.
 11. A method of forming a thin film according to claim 9, wherein the control of the time-mean of the rate of irradiation with said cluster ions is conducted by intermittently accelerating said cluster ions. 